|Publication number||US8034870 B2|
|Application number||US 11/012,800|
|Publication date||Oct 11, 2011|
|Priority date||Dec 17, 2003|
|Also published as||CN1894319A, CN100558800C, EP1697451A1, EP1697451B1, US20050137297, WO2005059018A1|
|Publication number||012800, 11012800, US 8034870 B2, US 8034870B2, US-B2-8034870, US8034870 B2, US8034870B2|
|Inventors||Gerrit de Wit|
|Original Assignee||Sabic Innovative Plastics Ip B.V.|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (115), Non-Patent Citations (15), Referenced by (2), Classifications (47), Legal Events (6)|
|External Links: USPTO, USPTO Assignment, Espacenet|
This application claims priority to U.S. Provisional Application Ser. No. 60/530,147 filed on Dec. 17, 2003, which is incorporated herein by reference in its entirety.
Thermoplastic polyester compositions, such as poly(alkylene terephthalates), have valuable characteristics including strength, toughness, high gloss, and solvent resistance. Polyesters therefore have utility as materials for a wide range of applications, from automotive parts to electric and electronic appliances. Because of their wide use, particularly in electronic applications, it is desirable to provide flame retardancy to polyesters. One particular set of conditions commonly accepted and used as a standard for flame retardancy is set forth in Underwriters Laboratories, Inc. Bulletin 94, which prescribes certain conditions by which materials are rated for self-extinguishing characteristics. Another set of conditions commonly accepted and used (especially in Europe) as a standard for flame retardancy is the Glow Wire Test (GWT), performed according to the International standard IEC 695-2-1/2. Numerous flame-retardants for polyesters are known, but many contain halogens, usually bromine. Halogenated flame retardant agents are less desirable because of the increasing demand for ecologically friendly ingredients. Halogen-free flame-retardants as Phosphorus and Nitrogen based compounds can be used as well, but they are lacking good flame retardancy for thin sections.
There is a need for polyester compositions having the combination of good flame retardant properties not only at thick nesses of >1.5 mm, but also at thick nesses at 0.8 mm or less and at least essentially maintaining mechanical properties and/or heat properties.
One or more of the above described drawbacks and disadvantages can be alleviated or minimized by a composition comprising: a polyester; a nitrogen-containing flame retardant selected from the group consisting of at least one of a triazine, a guanidine, a cyanurate, an isocyanurate, and mixtures thereof, a phosphinic acid salt and/or diphosphinic acid salt and/or their polymers; and a charring polymer.
Other embodiments, including a method of preparing the compositions, are described below.
According to an embodiment, a composition comprises a polyester such as a poly(butylene terephthalate); a nitrogen-containing flame retardant selected from the group consisting of at least one of a triazine, a guanidine, a cyanurate, an isocyanurate, and mixtures thereof, a phosphinic acid salt and/or diphosphinic acid salt and/or their polymers as described below; and a charring polymer.
Preferred polyesters are obtained by copolymerizing a glycol component and an acid component comprising at least about 70 mole %, preferably at least about 80 mole %, of terephthalic acid, or polyester-forming derivatives thereof. The preferred glycol, tetramethylene glycol, component can contain up to about 30 mole %, preferably up to about 20 mole % of another glycol, such as ethylene glycol, trimethylene glycol, 2-methyl-1,3-propane glycol, hexamethylene glycol, decamethylene glycol, cyclohexane dimethanol, neopentylene glycol, and the like, and mixtures comprising at least one of the foregoing glycols. The preferred acid component may contain up to about 30 mole %, preferably up to about 20 mole %, of another acid such as isophthalic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 4,4′-diphenyl dicarboxylic acid, 4,4′-diphenoxyethanedicarboxylic acid, sebacic acid, adipic acid, and the like, and polyester-forming derivatives thereof, and mixtures comprising at least one of the foregoing acids or acid derivatives.
A preferred polyester can have a number average molecular weight of about 10,000 atomic mass units (AMU) to about 200,000 AMU, as measured by gel permeation chromatography using polystyrene standards. Within this range, a number average molecular weight of at least about 20,000 AMU is preferred. Also within this range, a number average molecular weight of up to about 100,000 AMU is preferred, and a number average molecular weight of up to about 50,000 AMU is more preferred.
The polyester can be present in the composition at about 20 to about 90 weight percent, based on the total weight of the composition. Within this range, it is preferred to use at least about 25 weight percent, even more preferably at least about 30 weight percent of the polyester such as poly(butylene terephthalate).
In a further embodiment the composition can contain a second polyester resin that is different from the first polyester. For the second polyester, suitable resins include those derived from a C2-C10 aliphatic or cycloaliphatic diol, or mixtures thereof, and at least one aromatic dicarboxylic acid. Preferred polyesters are derived from an aliphatic diol and an aromatic dicarboxylic acid having repeating units of the following general formula (1):
wherein n is an integer of from 2 to 6, and R is a C6-C20 divalent aryl radical comprising a decarboxylated residue derived from an aromatic dicarboxylic acid.
Examples of aromatic dicarboxylic acids represented by the decarboxylated residue R are isophthalic acid, terephthalic acid, 1,2-di(p-carboxyphenyl)ethane, 4,4′-dicarboxydiphenyl ether, 4,4′-bisbenzoic acid, and the like, and mixtures thereof. All of these acids contain at least one aromatic nucleus. Acids containing fused rings can also be present, such as in 1,4-, 1,5-, or 2,6-naphthalene dicarboxylic acids. Preferred dicarboxylic acids include terephthalic acid, isophthalic acid, naphthalene dicarboxylic acids, and the like, and mixtures comprising at least one of the foregoing dicarboxylic acids.
The aliphatic or alicyclic polyols include glycols, such as ethylene glycol, propylene glycol, butanediol, hydroquinone, resorcinol, trimethylene glycol, 2-methyl-1,3-propane glycol, 1,4-butanediol, hexamethylene glycol, decamethylene glycol, 1,4-cyclohexane dimethanol, or neopentylene glycol.
Also contemplated herein are the above polyesters with minor amounts, e.g., about 0.5 to about 30 percent by weight, of units derived from aliphatic acids and/or aliphatic polyols to form copolyesters. The aliphatic polyols include glycols, such as poly(ethylene glycol). Such polyesters can be made following the teachings of, for example, U.S. Pat. Nos. 2,465,319 to Whinfield et al., and 3,047,539 to Pengilly.
Block copolyester resin components are also useful, and can be prepared by the transesterification of (a) straight or branched chain poly(alkylene terephthalate) and (b) a copolyester of a linear aliphatic dicarboxylic acid and, optionally, an aromatic dibasic acid such as terephthalic or isophthalic acid with one or more straight or branched chain dihydric aliphatic glycols. Especially useful when high melt strength is important are branched high melt viscosity resins, which include a small amount of, e.g., up to 5 mole percent based on the acid units of a branching component containing at least three ester forming groups. The branching component can be one that provides branching in the acid unit portion of the polyester, in the glycol unit portion, or it can be a hybrid branching agent that includes both acid and alcohol functionality. Illustrative of such branching components are tricarboxylic acids, such as trimesic acid, and lower alkyl esters thereof, and the like; tetracarboxylic acids, such as pyromellitic acid, and lower alkyl esters thereof, and the like; or preferably, polyols, and especially preferably, tetrols, such as pentaerythritol; triols, such as trimethylolpropane; dihydroxy carboxylic acids; and hydroxydicarboxylic acids and derivatives, such as dimethyl hydroxyterephthalate, and the like. Branched poly(alkylene terephthalate) resins and their preparation are described, for example, in U.S. Pat. No. 3,953,404 to Borman. In addition to terephthalic acid units, small amounts, e.g., from 0.5 to 15 mole percent of other aromatic dicarboxylic acids, such as isophthalic acid or naphthalene dicarboxylic acid, or aliphatic dicarboxylic acids, such as adipic acid, can also be present, as well as a minor amount of diol component other than that derived from 1,4-butanediol, such as ethylene glycol or cyclohexylenedimethanol, etc., as well as minor amounts of trifunctional, or higher, branching components, e.g., pentaerythritol, trimethyl trimesate, and the like.
The flame retardant polyester composition includes a flame retarding quantity of one or a mixture of nitrogen-containing flame retardants such as triazines, guanidines, cyanurates, and isocyanurates. Preferred triazines have the formula (2):
wherein R1, R2, and R3 are independently C1-C12 alkyl, C1-C12 alkoxyl, C6-C12 aryl, amino, C1-C12 alkyl-substituted amino, or hydrogen. Highly preferred triazines include 2,4,6-triamine-1,3,5-triazine (melamine, CAS Reg. No. 108-78-1), melamine derivatives, melam, melem, melon, ammeline (CAS Reg. No. 645-92-1), ammelide (CAS Reg. No. 645-93-2), 2-ureidomelamine, acetoguanamine (CAS Reg. No. 542-02-9), benzoguanamine (CAS Reg. No. 91-76-9), and the like. Salts/adducts of these compounds with boric acid or phosphoric acid may be used in the composition. Examples include melamine pyrophosphate and melamine polyphosphate. Preferred cyanurate/isocyanurate compounds include salts/adducts of the triazine compounds with cyanuric acid, such as melamine cyanurate and any mixtures of melamine salts.
Preferred guanidine compounds include guanidine; aminoguanidine; and the like; and their salts and adducts with boric acid, carbonic acid, phosphoric acid, nitric acid, sulfuric acid, and the like; and mixtures comprising at least one of the foregoing guanidine compounds.
The nitrogen-containing flame retardant may be present in the composition at about 1 to about 25 weight percent, based on the total weight of the composition. Within this range, it is preferred to use at least about 5 weight percent, even more preferably at least about 8 weight percent of the nitrogen-containing flame retardant. Also within this range, it is be preferred to use LIP to about 20 weight percent.
The nitrogen-containing flame-retardants are used in combination with one or more phosphinic acid salts. The phosphinates and diphosphinates include those set forth in U.S. Pat. No. 6,255,371 to Schosser et al. The specification of this patent, column 1, line 46 to column 3 line 4 is incorporated by reference into the present specification. Specific phosphinates mentioned include aluminum diethylphosphinate (DEPAL), and zinc diethylphosphinate (DEPZN). The phosphinates have the formula (I) [(R1)(R2)(PO)—O]m −Mm+ and formula II [(O—POR1)(R3)(POR2—O)]n 2−Mx m+, and or polymers comprising such formula I or II, where R1 and R2 are identical or different and are H, C1-C6-alkyl, linear or branched, and/or aryl; R3 is C1-C10, alkylene, linear or branched, C6-C10-arylene, -alkylarylene or -arylalkylene; M is any metal, but preferred are magnesium, calcium, aluminum or zinc, m is 1, 2 or 3; n is 1, 2 or 3; x is 1 or 2. The structures of formula I and II are specifically incorporated by reference from the Schosser patent into the present application. Note that R1 and R2 can be H, in addition to the substituents referred to set forth in the patent. This results in a hypophosphite, a subset of phosphinate, such as calcium hypophosphite, aluminum hypophosphite and the like.
The charring polymer is a polymer that has not more than about 85% weight loss at 400-500 degrees Centigrade upon heating under nitrogen using a thermogravimetric analysis (TGA) at a heating rate of 20 Centigrade degrees per minute. Typical charing polymers include polyetherimides, poly(phenylene ether), poly(phenylenesulfide), polysulphones, polyethersulphones, poly(phenylenesulphide oxide (PPSO), polyphenolics (e.g. Novolac). The charring polymer is present in an amount from about 0.1 to about 15 percent by weight of the composition.
The compositions may, optionally, further comprise a reinforcing filler. Suitable reinforcing fillers include silica; silicates such as talc or mica; carbon black; and reinforcing fibers, such as carbon fiber, aramide fiber, glass fiber, and the like; and mixtures comprising at least one of the foregoing fillers. In a preferred embodiment, the reinforcing filler comprises glass fibers. For compositions ultimately employed for electrical uses, it is preferred to use fibrous glass fibers comprising lime-aluminum borosilicate glass that is relatively soda free, commonly known as “E” glass. However, other glasses are useful where electrical properties are not so important, e.g., the low soda glass commonly known as “C” glass. The glass fibers may be made by standard processes, such as by steam or air blowing, flame blowing and mechanical pulling. Preferred glass fibers for plastic reinforcement may be made by mechanical pulling. The diameter of the glass fibers is generally about 1 to about 50 micrometers, preferably about 1 to about 20 micrometers. Smaller diameter fibers are generally more expensive, and glass fibers having diameters of about 10 to about 20 micrometers presently offer a desirable balance of cost and performance. The glass fibers may be bundled into fibers and the fibers bundled in turn to yarns, ropes or rovings, or woven into mats, and the like, as is required by the particular end use of the composition. In preparing the molding compositions, it is convenient to use the filamentous glass in the form of chopped strands of about one-eighth to about 2 inches long, which usually results in filament lengths between about 0.0005 to about 0.25 inch in the molded compounds. Such glass fibers are normally supplied by the manufacturers with a surface treatment compatible with the polymer component of the composition, such as a siloxane, titanate, or polyurethane sizing, or the like.
When present in the composition, the reinforcing filler may be used at about 10 to about 60 weight percent, based on the total weight of the composition. Within this range, it is preferred to use at least about 20 weight percent of the reinforcing filler. Also within this range, it is preferred to use up to about 50 weight percent, more preferably up to about 40 weight percent, of the reinforcing filler.
The composition can further comprise one or more anti-dripping agents, which prevent or retard the resin from dripping while the resin is subjected to burning conditions. Specific examples of such agents include silicone oils, silica (which also serves as a reinforcing filler), asbestos, and fibrillating-type fluorine-containing polymers. Examples of fluorine-containing polymers include fluorinated polyolefins such as, for example, poly(tetrafluoroethylene), tetrafluoroethylene/hexafluoropropylene copolymers, tetrafluoroethylene/ethylene copolymers, polyvinylidene fluoride, poly(chlorotrifluoroethylene), and the like, and mixtures comprising at least one of the foregoing anti-dripping agents. A preferred anti-dripping agent is poly(tetrafluroethylene). When used, an anti-dripping agent is present in an amount of about 0.02 to about 2 weight percent, and more preferably from about 0.05 to about 1 weight percent, based on the total weight of the composition.
The compositions may, optionally, further comprise other conventional additives used in polyester polymer compositions such as non-reinforcing fillers, stabilizers, mold release agents, plasticizers, and processing aids. Other ingredients, such as dyes, pigments, anti-oxidants, and the like can be added for their conventionally employed purposes.
The compositions can be prepared by a number of procedures. In an exemplary process, the polyester composition, optional amorphous additives, impact modifier and filler and/or reinforcing glass is put into an extrusion compounder with resinous components to produce molding pellets. The resins and other ingredients are dispersed in a matrix of the resin in the process. In another procedure, the ingredients and any reinforcing glass are mixed with the resins by dry blending, and then fluxed on a mill and comminuted, or extruded and chopped. The composition and any optional ingredients can also be mixed and directly molded, e.g., by injection or transfer molding techniques. Preferably, all of the ingredients are freed from as much water as possible. In addition, compounding should be carried out to ensure that the residence time in the machine is short; the temperature is carefully controlled; the friction heat is utilized; and an intimate blend between the resin composition and any other ingredients is obtained.
Preferably, the ingredients are pre-compounded, pelletized, and then molded. Pre-compounding can be carried out in conventional equipment. For example, after pre-drying the polyester composition (e.g., for about four hours at about 120° C.), a single screw extruder may be fed with a dry blend of the ingredients, the screw employed having a long transition section to ensure proper melting. Alternatively, a twin screw extruder with intermeshing co-rotating screws can be fed with resin and additives at the feed port and reinforcing additives (and other additives) may be fed downstream. In either case, a generally suitable melt temperature will be about 230° C. to about 300° C. The pre-compounded composition can be extruded and cut up into molding compounds such as conventional granules, pellets, and the like by standard techniques. The composition can then be molded in any equipment conventionally used for thermoplastic compositions, such as a Newbury type injection molding machine with conventional cylinder temperatures, at about 230° C. to about 280° C., and conventional mold temperatures at about 55° C. to about 95° C. The compositions provide an excellent balance of impact strength, and flame retardancy.
An additional preferred embodiment encompasses molded articles made from the composition, such as electric and electronic parts, including, for example, connectors, circuit breakers, and power plugs.
It should be clear that the invention encompasses reaction products of the above described compositions.
The invention is further illustrated by the following non-limiting examples.
All formulations are made by dry-blending of ingredients with the exception of tetraphenyl BPA-diphosphate (BPA-DP) and glass fiber. The blends are subsequently compounded on a Werner-Pfleiderer 25 mm co-rotating extruder, where BPA-DP and glass were fed separately downstream of the blend. The extruder temperature settings (upstream to downstream) were 50-140-265-260-260-260-260-260-275° C.; a vacuum of 0.45 bar was applied and the screw rotation rate was 300 RPM.
Molding of parts was performed on a 35 ton Engel injection molding machine with temperature settings of 245-255-265-265° C. (from throat to nozzle) and a mold temperature of 70° C. for the PBT-based formulations. Prior to molding the pellets were pre-dried at 120° C. for 2-4 hrs.
While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.
Test specimens were evaluated for Izod unnotched Impact (IUI) strength in accordance with ISO 180, and results are expressed in units of kJ/m2. UL94 testing was employed for the flame retardance testing. The tensile strength was evaluated using ISO527. The polybutylene terephthalate (PBT) employed was GE's PBT-315 and GE's PBT-195, used in the weight ratio of 2:1. MC-25 is melamine cyanurate from Ciba. TSAN is available from GE and is a fibrillating type Teflon in styrene acrylonitrile. BPA-DP is bisphenol A diphosphate from Albemarle. PPO is polyphenylene oxide from GE (polyphenylether of 2,6-xylenol). Ultem 1010 is polyetherimide from GE. Standard stabilizers are used such as Irganox 1010 and/or epoxy. Standard pigments employed include zinc sulfide.
The results of the different formulations are mentioned in the table.
UL @ 1.5
UL @ 0.8
retention after 1
week aging at 140 C.
Comparative samples A and B show that by using a P-compound as BPA-DP no good thermal stability good be obtained; the tensile strength retention after 1 week at 140 C is lower than 50%. For the formulations based on a phosphinate this retention is higher than 80%.
Samples 1 and 2, belonging to the invention show that the UL-performance at 0.8 mm is V0, in contrast with comparative sample C. So the addition of a charring polymer gives better UL-performance, while the tensile strength retention is still good. The charring polymer Ultem (Polyetherimide from GE) is preferred over PPO due to higher impact values.
Upon using lower amounts of melamine cyanurate it can be seen that the impact improves, but a charring polymer (formulation 3) is needed to maintain a V0 performance at 1.5 mm; the comparative samples D and E result only in a V1 performance. Upon further lowering the flame retardant amounts, in this case the phosphinate amount, it can be seen that the UL-performance drops to NC (non-classified) or NR (not-rated) for comparative sample F, but for sample 4 the material still has a V1 performance. Also in the case of calcium hypophosphite (calcium phosphinate) addition of a charring polymer (formulation 5) result in better UL-performance without negative effects on the tensile strength retention.
From the results it can be concluded that a combination of a phosphinate compound with a charring polymer, in the presence of a nitrogen compound, gives the best balance in properties as UL-performance and tensile strength retention upon oven aging. Without the charring agent or in case of another Phosphorus compound (as BPA-DP) these results could not be obtained.
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US2071250||Jul 3, 1931||Feb 16, 1937||Du Pont||Linear condensation polymers|
|US2071251||Mar 14, 1933||Feb 16, 1937||Du Pont||Fiber and method of producing it|
|US2130523||Jan 2, 1935||Sep 20, 1938||Du Pont||Linear polyamides and their production|
|US2130948||Apr 9, 1937||Sep 20, 1938||Du Pont||Synthetic fiber|
|US2241322||Feb 9, 1939||May 6, 1941||Du Pont||Process for preparing polyamides from cyclic amides|
|US2312966||Apr 1, 1940||Mar 2, 1943||Du Pont||Polymeric material|
|US2465319||Sep 24, 1945||Mar 22, 1949||Du Pont||Polymeric linear terephthalic esters|
|US2512606||Sep 12, 1945||Jun 27, 1950||Du Pont||Polyamides and method for obtaining same|
|US2720502||Oct 3, 1952||Oct 11, 1955||Eastman Kodak Co||Organo-metallic titanium catalysts for the preparation of polyesters|
|US2727881||Oct 3, 1952||Dec 20, 1955||Eastman Kodak Co||Organo-titanium catalysts for the preparation of polyesters|
|US2822348||Nov 14, 1951||Feb 4, 1958||Du Pont||Ester interchange catalysts|
|US3047539||Nov 28, 1958||Jul 31, 1962||Goodyear Tire & Rubber||Production of polyesters|
|US3078254||Jul 20, 1959||Feb 19, 1963||Phillips Petroleum Co||High molecular polymers and method for their preparation|
|US3224043||Mar 15, 1963||Dec 21, 1965||Lego Nederland Nv||Injection moulding machines|
|US3265765||Jan 29, 1962||Aug 9, 1966||Shell Oil Co||Block polymers of monovinyl aromatic hydrocarbons and conjugated dienes|
|US3297793||Dec 21, 1962||Jan 10, 1967||Phillips Petroleum Co||Continuous process for producing block copolymers of dienes and vinyl aromatic compounds|
|US3302243||Apr 16, 1964||Feb 7, 1967||Herbert P Ludwig||Apparatus for the injection molding of plastic articles especially shoes|
|US3402159||Dec 20, 1963||Sep 17, 1968||Phillips Petroleum Co||Process for polymerizing butadiene and styrene terminated in short blocks of polystyrene|
|US3405198||Nov 22, 1966||Oct 8, 1968||Glanzstoff Ag||Process for making impact resistant injection molded polyethylene terephthalate products|
|US3594452||Feb 6, 1968||Jul 20, 1971||Shell Oil Co||Polymers prepared from monolithiumterminated block copolymers and certain diesters|
|US3671487||May 5, 1971||Jun 20, 1972||Gen Electric||Glass reinforced polyester resins containing polytetrafluoroethylene and flame retardant additives|
|US3769260||Jun 13, 1972||Oct 30, 1973||Allied Chem||Impact-resistant polyethylene terephthalate compositions|
|US3864428||Aug 27, 1973||Feb 4, 1975||Teijin Ltd||Polyester/polycarbonate/graft copolymer thermoplastic resin composition|
|US3915608||Oct 29, 1974||Oct 28, 1975||Ladislav Hujik||Injection molding machine for multi-layered shoe soles|
|US3953394||Nov 15, 1971||Apr 27, 1976||General Electric Company||Polyester alloys and molding compositions containing the same|
|US3953404||Feb 7, 1974||Apr 27, 1976||General Electric Company||Solid state polymerization of poly(1,4-butylene terephthalate)|
|US4096156||Nov 23, 1976||Jun 20, 1978||Hoechst Aktiengesellschaft||Process for the catalytic manufacture of γ-butyrolactone|
|US4119607||Mar 7, 1978||Oct 10, 1978||Shell Oil Company||Multicomponent polyester- block copolymer- polymer blends|
|US4128526||Dec 23, 1976||Dec 5, 1978||General Electric Company||Copolyesters of poly(alkylene glycol aromatic acid esters) and diesters comprising aromatic diols|
|US4141927 *||May 22, 1975||Feb 27, 1979||General Electric Company||Novel polyetherimide-polyester blends|
|US4154775||Sep 6, 1977||May 15, 1979||General Electric Company||Flame retardant composition of polyphenylene ether, styrene resin and cyclic phosphate|
|US4172859||May 23, 1975||Oct 30, 1979||E. I. Du Pont De Nemours And Company||Tough thermoplastic polyester compositions|
|US4180494||Sep 20, 1978||Dec 25, 1979||Rohm And Haas Company||Thermoplastic polyesters|
|US4254011||Nov 19, 1979||Mar 3, 1981||Bayer Aktiengesellschaft||Flame retarded polyethylene terephthalate compositions with improved drip suppression|
|US4264487||Sep 7, 1979||Apr 28, 1981||Rohm And Haas Company||Acrylate rubber modification of aromatic polyesters|
|US4292233||Jul 2, 1980||Sep 29, 1981||Bayer Aktiengesellschaft||High-impact polybutylene terephthalate|
|US4327764||May 21, 1980||May 4, 1982||Superpressure, Inc.||Float valve assembly for a liquid drain trap|
|US4364280||Jan 9, 1981||Dec 21, 1982||Kutsay Ali U||Double shear beam strain gage load cell|
|US4504613||Aug 19, 1983||Mar 12, 1985||General Electric Company||Polyphenylene ether resin compositions having improved ductile impact strength|
|US4506043||Apr 8, 1983||Mar 19, 1985||Teijin Limited||Glass fiber-reinforced thermoplastic polyester composition|
|US4940745||Oct 7, 1988||Jul 10, 1990||Basf Aktiengesellschaft||Glass fiber reinforced flameproofed thermoplastic molding compositions based on polyesters and graft polymers|
|US4954540||Mar 3, 1988||Sep 4, 1990||Polyplastics Co., Ltd.||Halogen-contained polyester resin composite and electric wire|
|US4983660||Dec 23, 1988||Jan 8, 1991||Mitsubishi Rayon Company Ltd.||Polyethylene terephthalate resin composition|
|US5302645||Jul 30, 1992||Apr 12, 1994||Mitsubishi Petrochemical Co., Ltd.||Polyethylene terephthalate composition|
|US5326806||Dec 23, 1992||Jul 5, 1994||General Electric Company||Reinforced flame-retardant polyester resin compositions|
|US5385970 *||Jul 30, 1993||Jan 31, 1995||General Electric Company||Halogen-free flame retardant ternary blends|
|US5684071 *||Jun 27, 1996||Nov 4, 1997||Kanegafuchi Kagaku Kogyo Kabushiki Kaisha||Additive for thermpolastic resins and flame retardant resin composition|
|US5955565||Dec 23, 1997||Sep 21, 1999||Eastman Chemical Company||Polyesters from terephthalic acid, 2,2,4,4-tetramethyl-1,3-cyclobutanediol and ethylene glycol|
|US6013707||Jun 9, 1998||Jan 11, 2000||Ticona Gmbh||Flameproofed polyester molding compositions|
|US6068935||Sep 23, 1999||May 30, 2000||Sumitomo Electric Industries, Ltd.||Thermoplastic polyester resin, and insulated wire, electrically insulated cable and heat-shrinkable tube each made with the resin|
|US6111031||Dec 9, 1997||Aug 29, 2000||General Electric Company||Filled polyetherimide resin compositions|
|US6150473||Dec 14, 1998||Nov 21, 2000||General Electric Company||Polyetherimide resin/polyester resin blends having improved properties|
|US6166114||Aug 13, 1998||Dec 26, 2000||E. I. Du Pont De Nemours And Company||Fire and electrical resistant compositions|
|US6255371 *||Jul 17, 2000||Jul 3, 2001||Clariant Gmbh||Flame-retardant combination|
|US6410607||Jan 5, 2000||Jun 25, 2002||Eastman Chemical Company||Glycolysis process for recycling of post-consumer pet|
|US6420459 *||Jan 25, 2000||Jul 16, 2002||Clariant Gmbh||Flame-retarding thermosetting compositions|
|US6429243||Jun 15, 1998||Aug 6, 2002||Kuraray Co., Ltd.||Polyester resin composition|
|US6444283||Jul 31, 2000||Sep 3, 2002||Eastman Chemical Company||Polyester-polyamide blends with reduced gas permeability and low haze|
|US6469095||Dec 4, 1997||Oct 22, 2002||Basf Aktiengesellschaft||Flame-proofed molding materials|
|US6503988||Nov 8, 1996||Jan 7, 2003||Daikin Industries, Ltd.||Polytetrafluoroethylene fine powders and their use|
|US6531530 *||Dec 21, 2000||Mar 11, 2003||Daicel Chemical Industries, Ltd.||Non halogen, organic or inorganic flame retardants in thermoplastic polymer blends|
|US6538054||Oct 16, 1997||Mar 25, 2003||Basf Aktiengesellschaft||Flame-proof moulding compounds|
|US6547992||Jan 29, 2000||Apr 15, 2003||Clariant Gmbh||Flame retardant combination for thermoplastic polymers l|
|US6569928||Feb 18, 2000||May 27, 2003||Akzo Nobel N.V.||Phosphorus-containing fire retardant thermoplastic polyester composition|
|US6794463||Mar 28, 2001||Sep 21, 2004||Asahi Kasei Kabushiki Kaisha||Block copolymer|
|US7063889||Sep 18, 2003||Jun 20, 2006||Jfe Steel Corporation||Resin film and manufacturing method for the same, and resin laminated metal sheet using said resin film and manufacturing method for the same|
|US7105589||Apr 22, 2003||Sep 12, 2006||Basf Aktiengesellschaft||Flame-resistant black thermoplastic molded masses|
|US7169836||Jun 27, 2002||Jan 30, 2007||Polyplastics Co., Ltd||Flame-retardant resin composition|
|US7498368||May 25, 2004||Mar 3, 2009||Polyplastics Co., Ltd.||Flame-retardant resin composition|
|US20010007888||Dec 21, 2000||Jul 12, 2001||Takayuki Asano||Flame retardant resin composition|
|US20010009944 *||Jun 30, 1998||Jul 26, 2001||General Electric Company||Polyester molding composition|
|US20020096669||Nov 27, 2001||Jul 25, 2002||Van Der Spek Pieter A.||Halogen-free flame-retardant composition|
|US20020111403 *||Dec 15, 2000||Aug 15, 2002||Gosens Johannes Cornelis||Flame retardant polyester compositions|
|US20020123566||Dec 20, 2000||Sep 5, 2002||Georgiev Emil M.||Flame retardant carbonate polymer composition|
|US20020134771||Jan 5, 2001||Sep 26, 2002||Richard Wenger||Flame-retarded laser-markable polyester composition|
|US20030018107||Mar 21, 2002||Jan 23, 2003||Wouter Heinen||Flame-retardant mixture|
|US20040072929||Jun 27, 2002||Apr 15, 2004||De Schryver Daniel A.||Flame retardant compositions|
|US20040192812||Jul 26, 2002||Sep 30, 2004||Jochen Engelmann||Halogen-free flameproof polyester|
|US20050137297||Dec 15, 2004||Jun 23, 2005||General Electric Company||Flame-retardant polyester composition|
|US20050137300||Dec 17, 2004||Jun 23, 2005||Clariant Gmbh||Flame retardant and stabilizer combined, for polyesters and polyamides|
|US20050143503||Oct 6, 2004||Jun 30, 2005||Clariant Gmbh||Phosphorus-containing flame retardant agglomerates|
|US20050154099||Sep 8, 2004||Jul 14, 2005||Toshikazu Kobayashi||Flame resistant polyester resin compositions|
|US20050191483||Sep 18, 2003||Sep 1, 2005||Jfe Steel Corporation||Resin film and manufacturing method for the same, and resin laminated metal sheet using said resin film and manufacturing method for the same|
|US20050272839||Jun 2, 2005||Dec 8, 2005||Clariant Gmbh||Compression-granulated flame retardant composition|
|US20060058431||Sep 14, 2004||Mar 16, 2006||Herve Cartier||Radiation crosslinking of halogen-free flame retardant polymer|
|US20060084734||May 11, 2005||Apr 20, 2006||Clariant Gmbh||Dialkylphosphinic salts, their use, and a process for their preparation|
|US20060247339||May 25, 2004||Nov 2, 2006||Polyplastics Co., Ltd.||Flame-retardant resin composition|
|US20070049667||Aug 31, 2005||Mar 1, 2007||General Electric Company||High flow polyester composition|
|US20070161725||Jan 28, 2005||Jul 12, 2007||Janssen Robert H C||Halogen-free flame-retarded polyester composition|
|US20080090950||Jun 10, 2004||Apr 17, 2008||Italmatch Chemicals||Polyester Compositions Flame Retarded With Halogen-Free Additives|
|US20080139711||Oct 11, 2007||Jun 12, 2008||Sabic Innovative Plastics Ip Bv||Polyester Compositions, Method Of Manufacture, And Uses Thereof|
|US20080242789||May 7, 2008||Oct 2, 2008||Yantao Zhu||Polymer Compositions, Method of Manufacture, and Articles Formed Therefrom|
|US20080269383||May 18, 2005||Oct 30, 2008||Ciba Specialty Cemicals Holding Inc.||Flame-Retardants|
|US20090124733||Sep 25, 2006||May 14, 2009||Wintech Polymer Ltd.||Flame retardant polybutylene terephthalate resin composition|
|US20090203871||Dec 15, 2006||Aug 13, 2009||Toyo Boseki Kabushiki Kaisha||Method for producing thermoplastic polyester elastomer, thermoplastic polyester elastomer composition, and thermoplastic polyester elastomer|
|DE19904814A1||Feb 5, 1999||Aug 10, 2000||Basf Ag||Low-migration moulding material for production of fire-resistant fibres, film and mouldings contains a blend of polyester and polycarbonate plus a metal phosphinate salt and possibly other additives|
|EP0146104A2||Dec 10, 1984||Jun 26, 1985||Mobay Corporation||Polyester thermoplastic molding compositions with good mold release|
|EP0672717A1||Mar 14, 1995||Sep 20, 1995||Toray Industries, Inc.||Flame-retardant polymer composition and shaped article thereof|
|EP0899303A2||Aug 26, 1998||Mar 3, 1999||General Electric Company||Polycarbonate molding compositions|
|EP0919591A1||Jun 15, 1998||Jun 2, 1999||Polyplastics Co. Ltd.||Flame-retardant thermoplastic polyester resin composition|
|EP1024168A1||Dec 24, 1999||Aug 2, 2000||Clariant GmbH||Flameretardant duroplastic masses|
|EP1070754A2||Jul 5, 2000||Jan 24, 2001||Clariant GmbH||Flame protecting combination|
|EP1967549A1||Dec 25, 2006||Sep 10, 2008||Wintech Polymer Ltd.||Flame-retardant resin composition for transmission side member in laser welding|
|GB1264741A||Title not available|
|JP4345655A||Title not available|
|JPH04345655A||Title not available|
|WO2000/49077A1||Title not available|
|WO2001/81470A1||Title not available|
|WO1999002606A1||Apr 22, 1998||Jan 21, 1999||Dsm N.V.||Halogen-free flame-retardant thermoplastic polyester or polyamide composition|
|WO1999065987A1||Jun 15, 1998||Dec 23, 1999||Kuraray Co., Ltd.||Polyester resin compositions|
|WO2005059018A1||Dec 16, 2004||Jun 30, 2005||General Electric Company||Flame-retardant polyester composition|
|WO2007084538A2||Jan 17, 2007||Jul 26, 2007||General Electric Company (A New York Corporation)||Ignition resistant polycarbonate polyester composition|
|WO2008011940A1||Jun 18, 2007||Jan 31, 2008||Dsm Ip Assets B.V.||Toughened halogen free flame retardant polyester composition|
|WO2008014254A2||Jul 24, 2007||Jan 31, 2008||Sabic Innovative Plastics Ip B.V.||Elastomer blends of polyesters and copolyetheresters derived from polyethylene terephthalate, method of manufacture, and articles therefrom|
|WO2008014273A1||Jul 24, 2007||Jan 31, 2008||Sabic Innovative Plastics Ip B.V.||Elastomer blends containing polycarbonates and copolyetheresters derived from polyethylene terephthalate, method of manufacture, and articles therefrom|
|1||ASTM D256-04; Standard Test Methods for Determining the Izod Pendulum Impact Resistance of Plastics.|
|2||ASTM Designation: D 256-06, "Standard Test Methods for Determining the Izod Pendulum Impact Resistance of Plastics," pp. 1-20 (2006).|
|3||ASTM Designation: D 648-06, "Standard Test Method for Deflection Temperature of Plastics Under Flexural Load in the Edgewise Position," pp. 1-13 (2006).|
|4||Chemical Processing, [online]; [retrieved on Oct. 14, 2009]; retrieved from the Internet http://www.chemicalprocessing.com/industrynews/2006/056.html Article: "GE gives plastic bottle recycling a new spin," Chemical Processing.com, Aug. 26, 2006, 2pgs.|
|5||Cooper, et al., "Life Cycle Engineering Guidelines," EPA 600/R-01/101, Risk Management Research, pp. 1-100 (2001).|
|6||International Preliminary Report on Patentability & Written Opinion, International Application No. PCT/US2004/042202; International Filing Date Dec. 16, 2004; Date of Mailing Jun. 20, 2006; 5 pages.|
|7||International Seach Report & Written Opinion, International Application No. PCT/US2008/066599, International Filing Date Jun. 11, 2008, mailed Mar. 2, 2009, 7 pages.|
|8||International Search Report & Written Opinion, International Application No. PCT/US2004/042202; International Filing Date Dec. 16, 2004; Date of Mailing Mar. 9, 2005; 12 pages.|
|9||International Search Report & Written Opinon, International Application No. PCT/US2008/066603, International Filing Date Jun. 11, 2008, Date of Mailing Mar. 12, 2009; 13 pages.|
|10||International Standard: ISO 180, "Plastics-Determination of Izod Impact Strength," pp. 1-16 (2000).|
|11||International Standard: ISO 180, "Plastics—Determination of Izod Impact Strength," pp. 1-16 (2000).|
|12||International Standard: ISO 527-1, "Plastics-Determination of Tensile Properties," pp. 1-54 (1993).|
|13||International Standard: ISO 527-1, "Plastics—Determination of Tensile Properties," pp. 1-54 (1993).|
|14||*||STN Search Report pp. 1-3.|
|15||UL 94, "Tests for Flammability of Plastic Materials for Parts in Devices and Appliances," 52 pgs., (Dec. 12, 2003).|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US20110180300 *||Sep 25, 2009||Jul 28, 2011||Polyone Corporation||Flame retardant thermoplastic elastomers|
|US20110229673 *||Sep 22, 2011||Konica Minolta Business Technologies, Inc.||Flame-retardant polyester resin composition and blow molded container|
|U.S. Classification||524/513, 524/612, 524/430, 524/196, 524/601, 524/100, 524/115, 524/424, 524/451, 524/126, 524/186|
|International Classification||C08G18/77, C08L79/08, C08K3/00, C08J3/22, C08L81/06, C08K5/34, B01F17/00, C08L71/12, C08L67/02, C08G18/48, B32B7/12, C08L61/06, C08L81/04, C07F9/48, C08K3/18, C08F283/02, C08G67/02, C08L67/00, C08K5/00, C08K5/3492, C08K5/5313, C08K5/31|
|Cooperative Classification||C08K5/31, C08L67/02, C08K5/0066, C08L81/06, C08K3/0058, C08K5/34924, C08K5/3492, C08L81/04, C08K5/5313, C08K5/34928, C08L79/08, C08L71/12, C08L61/06|
|Dec 15, 2004||AS||Assignment|
Owner name: GENERAL ELECTRIC COMPANY, NEW YORK
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:DE WIT, GERRIT;REEL/FRAME:016099/0502
Effective date: 20041214
|May 1, 2008||AS||Assignment|
Owner name: SABIC INNOVATIVE PLASTICS IP B.V., NETHERLANDS
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:GENERAL ELECTRIC COMPANY;REEL/FRAME:020985/0551
Effective date: 20070831
Owner name: SABIC INNOVATIVE PLASTICS IP B.V.,NETHERLANDS
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:GENERAL ELECTRIC COMPANY;REEL/FRAME:020985/0551
Effective date: 20070831
|Aug 18, 2008||AS||Assignment|
Owner name: CITIBANK, N.A., AS COLLATERAL AGENT, NEW YORK
Free format text: SECURITY AGREEMENT;ASSIGNOR:SABIC INNOVATIVE PLASTICS IP B.V.;REEL/FRAME:021423/0001
Effective date: 20080307
Owner name: CITIBANK, N.A., AS COLLATERAL AGENT,NEW YORK
Free format text: SECURITY AGREEMENT;ASSIGNOR:SABIC INNOVATIVE PLASTICS IP B.V.;REEL/FRAME:021423/0001
Effective date: 20080307
|Mar 17, 2014||AS||Assignment|
Owner name: SABIC INNOVATIVE PLASTICS IP B.V., NETHERLANDS
Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:CITIBANK, N.A.;REEL/FRAME:032459/0798
Effective date: 20140312
|Mar 25, 2015||FPAY||Fee payment|
Year of fee payment: 4
|Jun 6, 2016||AS||Assignment|
Owner name: SABIC GLOBAL TECHNOLOGIES B.V., NETHERLANDS
Free format text: CHANGE OF NAME;ASSIGNOR:SABIC INNOVATIVE PLASTICS IP B.V.;REEL/FRAME:038883/0816
Effective date: 20140402